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Chemical Engineering and Processing 46 (2007) 13171323

Esterification of acetic acid with ethanol: Reaction kinetics and

operation in a packed bed reactive distillation column
N. Calvar, B. Gonzalez, A. Dominguez
Chemical Engineering Department, University of Vigo, 36310 Vigo, Spain
Received 13 February 2006; received in revised form 18 September 2006; accepted 12 October 2006
Available online 20 November 2006

Abstract
The reaction kinetics of the esterification of acetic acid with ethanol, catalyzed both homogeneously by the acetic acid, and heterogeneously
by Amberlyst 15, have been investigated. The reactions were carried out at several temperatures between 303.15 and 353.15 K and at various
starting reactant compositions. Homogeneous and heterogeneous reactions have been described using the models proposed by Popken et al.
[T. Popken, L. Gotze, J. Gmehling, Reaction kinetics and chemical equilibrium of homogenously and heterogeneously catalyzed acetic acid
esterification with methanol and methyl acetate hydrolysis, Ind. Eng. Chem. Res. 39 (2000) 26012611]. These models use activities instead of
mole fractions. Activity coefficients have been calculated using ASOG [K. Kojima, K. Tochigi, Prediction of Vaporliquid Equilibria by the ASOG
Method, Elsevier, Tokyo, 1979] and UNIFAC (Aa. Fredenslund, J. Gmehling, P. Rasmussen, Vaporliquid Equilibria Using UNIFAC. A Group
Contribution Method, Elsevier, Amsterdam, 1977] methods.
A packed bed reactive distillation column filled with Amberlyst 15 has been employed to obtain ethyl acetate. The influence of feed composition
and reflux ratio have been analyzed.
2006 Elsevier B.V. All rights reserved.

Keywords: Reactive distillation; Kinetics; Ethyl acetate production

1. Introduction distillation column are presented. The above mentioned kinet-

Reactive distillation has become an interesting alternative to
some conventional processes, especially for equilibrium-limited
reactions as esterifications and etherifications. In these reactions,
conversion and selectivity are increasing because products are
continuously removed from the reaction mixture. In last years,
investigations of thermodynamic, reaction kinetics and simula-
tion for different processes have been made (Bock et al. [4], Vora
and Daoutidis [5], Kenig et al. [6], Steinigeweg and Gmehling
[7], Teo and Saha [8], Kloker et al. [9]). The aim of this work
is the study of the production of ethyl acetate by esterification
of acetic acid with ethanol in a reactive distillation column. In
a previous work (Calvar et al. [10]) the vaporliquid equilibria
of the quaternary reactive system acetic acid + ethanol + ethyl
acetate + water at 101.3 kPa have been determined. In this paper,
the homogenous and heterogeneous catalyzed esterification
kinetics and the results of the operation in a packed bed reactive
ics have been studied previously by Kirbaslar et al. [11] and
Hangx et al. [12] but they did not take into account the activity
coefficient of the compounds in the mixture.
2. Experimental
2.1. Chemicals
Acetic acid was supplied by Sigma and ethanol and ethyl
acetate were supplied by Merck. The components were degassed
Aldrich),
ultrasonically, dried over molecular sieves (type 4 A,
and kept in an inert argon with a maximum water content
of 2 106 mass fraction. Their mass fraction purities were
>99 mass% for acetic acid and >99.8 mass% for methanol,
ethanol and ethyl acetate. The water was bidistillated and
deionized.
2.2. Catalyst

Corresponding author. Tel.: +34 986812422; fax: +34 986812387. The catalyst used was an ion-exchange resin Amberlyst 15
E-mail address: admguez@uvigo.es (A. Dominguez). supplied by Supelco. The catalyst was washed with ethanol and

0255-2701/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2006.10.007
1318 N. Calvar et al. / Chemical Engineering and Processing 46 (2007) 13171323

water to remove impurities and dried at 363.15 K. Mean diameter

of the resin beads, obtained by scanning electron microscopy, is
7.6 103 m.

2.3. Analysis

A Hewlett-Packard 6890GC chromatograph was used to

determine the composition of the samples. The gas chromato-
graph column was HP-FFAP polyethylene glycol TPA equipped
with series of connected thermal conductivity and flame ion-
ization detectors to detect water and the other compounds in
the same run. Helium was used as carrier at a flow rate of
6.8 108 m3 s1 . Injector, detectors and oven temperature
were 473.15, 503.15 and 423.15 K, respectively. To know the
composition of these quaternary mixtures it is necessary to have
quaternary patrons of known composition, so 249 quaternary
mixtures were prepared by mass and were measured by gas chro-
matography.

3. Results and discussion

The experiments were performed in a stirred glass reactor

with a volume of 1.5 104 m3 . The temperature in the reactor
was maintained within 0.1 K. The acetic acid and the cata-
lyst were heated at reaction temperature, ethanol was heated
separately. When temperature reaction is reached, the second
reactant was added to the mixture in the reactor and this was
considered the starting time of the reaction. During each exper-
iment, samples of about 5 107 m3 were taken and cooled to
avoid vaporization before analyzing.

3.1. Reaction kinetics: homogeneous reaction

The homogeneous reactions, esterification or hydrolysis, are Fig. 1. Homogeneous kinetic. (a) Effect of temperature for equimolar reactant
ratio. (b) Effect of reactant molar on the ethyl acetate conversion at 303.15 K.
catalyzed by the acetic acid. Table 1 summarizes the experiments
made at 303.15, 323.15 and 353.15 K. The duration of each
experiment to reach chemical equilibrium is indicated in the Fig. 1 shows the influence of temperature and molar reactant
third column. ratio on ethyl acetate conversion. The increase in temperature
gives an increase in equilibrium conversion and in reaction rate
Table 1 for esterification and hydrolysis reactions. Conversion increases
Summary of the homogeneous reaction experiments from 50% at 303.15 K to 84% at 353.15 K in esterification reac-
Run T (K) Esterification molar ratio: Duration tion and from 10% at 323.15 K to 65% at 353.15 for hydrolysis.
acetic acid/ethanol (days) The use of an excess of acetic acid increases the conversion
1 303.15 0.85 105
because the reaction is catalyzed by the acid. The equilibrium
2 303.15 1.00 95 conversion increases from around 45% at an acetic acid/ethanol
3 303.15 1.15 90 molar ratio of 0.8575% at a molar ratio of 1.6 at 303.15 K.
4 303.15 1.30 63 Experimental data were fitted using the following equation
5 303.15 1.60 93 (Popken et al. [1])
6 323.15 1.00 22
7 323.15 1.60 26 dX
8 353.15 1.00 13 r = n0 = aHAc (k1 aHAc aEtOH k1 aEtAc aH2 O ) (1)
9 353.15 1.60 10 dt

Run T (K) Hydrolysis molar ratio: Duration

where can take the values of 0.5 or 1 when the autocatalysis
water:ethyl acetate:acetic acid (days) mechanism is via the solvated protons of the dissociated acid or
via the molecular acid, respectively. Activities were calculated
10 323.15 1.0:1.0:1.5 59
11 353.15 1.0:1.0:1.5 19
using ASOG [2] and UNIFAC [3] methods, to calculate activity
coefficients, and assuming an ideal behaviour.
 N. Calvar et al. / Chemical Engineering and Processing 46 (2007) 13171323 1319

Estimation of kinetic parameters, k1 and k1 , were performed

by minimizing the sum of squared residuals between the exper-
imental and calculated reaction rates,


NDAT
SRS = (ri,exp ri,calc )2 (2)
i=1

Experimental acetic acid weight fraction data were compared

with predicted ones through the mean relative deviation (MRD),
NDAT  
1   wHAc,exp wHAc,calc 
MRD =   100 (3)
NDAT  wHAc,exp 
i=1

Table 2 shows SRS and MRD values using ASOG or UNI-

FAC methods to calculate activity coefficients. Best results were
obtained using ASOG method and = 1. Surprisingly, assuming
an ideal behaviour of the liquid phase SRS and MRD are lower Fig. 2. Arrhenius diagrams of the rate constants for the esterification and hydrol-
than using UNIFAC method. In addition, it is noteworthy that ysis reaction of the homogeneous reaction.
the difference of the different fittings using ASOG, UNIFAC and
Table 3
ideal behaviour of the liquid phase, is not large in spite the non- Preexponential factors and activation energies of esterification and hydrolysis
ideal behaviour of the studied system. This can be owed to the calculated by ASOG and UNIFAC
activity coefficients of the acetic acid calculated with the differ-
Homogeneous Heterogeneous
ent methods, since the activity of this compound has more weight
in the equation we use (Eq. (1)). Using the ASOG method, the ASOG UNIFAC ASOG UNIFAC
activity coefficients of the acetic acid is always less than one, EA,1 (kJ mol1 ) 41.43 53.74 38.40 28.49
while using UNIFAC method these coefficients are always more EA,1 (kJ mol1 ) 30.06 60.50 35.07 26.70
than one, although the difference among them is small. k10 (mol s1 ) 65.75 3317.28
The temperature dependence of the rate constants is k1
0
(mol s1 ) 0.06 4619.43
k10 103 (mol s1 kg1 ) 161.29 2.811
expressed by the Arrhenius law,
k1
0
103 (mol s1 kg1 ) 8.34 0.051
 
Ea,i
ki = ki exp
0
(4)
RT
3.2. Reaction kinetics: heterogeneous reaction
For the case of = 1 and liquid phase activities calculated by
ASOG and UNIFAC, using the parameters k1 and k1 estimated Amberlyst 15 is a catalyst widely used in esterification reac-
previously, we can calculate the preexponential factors and acti- tions (Popken et al. [1], Mazzotti et al. [13], Sanz et al. [14])
vation energies of esterification and hydrolysis. The Arrhenius and it can be easily supported in different types of packing as
diagrams for both fits are presented in Fig. 2. Katapak-S for reactive distillation. Chakrabarti and Sharma [15]
Table 3 summarizes the kinetic parameters using ASOG and
UNIFAC models and = 1. Fig. 3 shows experimental and fit-
ted acetic acid concentration values at several temperatures and
different molar reactant ratios.

Table 2
Sum of squared residuals, SRS, and mean relative deviation, DMR, of the differ-
ent models used to fit homogeneous and heterogeneous reaction experimental
data
Activities SRS 104 DMR (%)

Homogeneous ASOG 0.5 3.3 3.3

1 2.1 2.4
UNIFAC 0.5 4.3 4.4
1 3.2 3.8
Ideal 0.5 3.8 3.8
1 2.7 3.2
Heterogeneous ASOG 0.02 7.8
UNIFAC 0.02 11.5 Fig. 3. Homogeneous kinetic. Comparison between experimental and calculated
Ideal 0.03 9.6 weight fraction of acetic acid, activity coefficients calculated by () ASOG and
(- - -) UNIFAC.
1320 N. Calvar et al. / Chemical Engineering and Processing 46 (2007) 13171323

Table 4 ratio. Conversion increases from 55 to 65% when temperature

Summary of the experiments catalyzed by Amberlyst 15 increases. As it can be observed, for catalytic reaction, conver-
Run T (K) Catalyst (g) Molar ratio acetic Duration (min) sion is lower than in an autocatalyzed one, because these resins
acid/ethanol not only act as catalyst but also affect the equilibrium conver-
12 323.15 5 0.6 380 sion due to their selective adsorption of reactants and swelling
13 323.15 5 1.0 285 nature [17,18]. When temperature increases, the rate of hydrol-
14 323.15 5 1.6 275 ysis reaction is higher than the esterification rate.
15 338.15 5 1.0 210 The use of an excess of acetic acid increase the conversion
16 338.15 5 1.6 202
17 353.15 5 0.6 235
even if the reaction is catalyzed by Amberlyst 15. The equi-
18 353.15 5 1.0 190 librium conversion increases from around 4081% when acetic
19 353.15 5 1.6 165 acidethanol molar ratio increases from 0.6 to 1.6, at 353.15 K.
20 353.15 7.5 1.0 185 The pseudohomogeneous model (Popken et al. [1]) has been
considered for the heterogeneous reaction,

show that external diffusion does not usually control the overall
rate in the reactions catalyzed by ion-exchange resins, unless the
agitation is very low, or the mixture is very viscous. All the exper-
iments were performed at a stirrer speed of 500 rpm (Table 4). In
literature [1,14,16] was found that in the most part of the hetero-
geneous reactions catalyzed by Amberlyst, the internal diffusion
limitation is insignificant, so the resins are used without sieving.
Experiments were carried out at 323.15, 338.15 and 353.15 K.
Fig. 4 shows the influence of temperature and molar reactant
n0 dX
r= = (k1 aHAc aEtOH k1 aEtAc aH2 O ) (5)
mcat dt
where n0 is the initial number of acetic acid moles and mcat is
the catalyst mass.
Experimental and calculated reaction rates have been
obtained using ASOG and UNIFAC method to calculate activ-
ity coefficients. The best fit has been obtained using the ASOG
method (Table 2). In Fig. 5 the Arrhenius diagram is shown.
Table 3 summarizes kinematic parameter values. Fig. 6 shows
experimental and fitted values of acetic acid concentration at
several temperatures and molar reactant ratios.

3.3. Reactive distillation column

The reaction was carried out in a distillation column and the

reaction conversion and separation degree have been analyzed.
Pure components and azeotropes normal boiling points and com-
position of the different azeotropes present in this quaternary
system (Kenig et al. [6]) are shown in Table 5.
The experiments were performed in a glass column with an
inner diameter of 0.05 m and three packing sections with an
height of 0.15, 0.60 and 0.15 m, respectively (Fig. 5). Lower
and upper sections are packed with Multiknit supplied by Tiss-
metal. Intermediate section is the reactive section and it is packed

Fig. 4. Heterogeneous kinetic. (a) Effect of temperature for equimolar reactant

ratio. (b) Effect of molar ratio of acetic acid and ethanol on the ethanol conversion Fig. 5. Arrhenius diagrams of the rate constants for the esterification and hydrol-
at 323.15 K. ysis reaction of the heterogeneous reaction.
 N. Calvar et al. / Chemical Engineering and Processing 46 (2007) 13171323 1321

Fig. 6. Heterogeneous kinetic. Comparison between experimental and calcu-

lated weight fraction of acetic acid, activity coefficients calculated by () ASOG
and (- - -) UNIFAC.

with Amberlyst 15 supported on Katapak-S (Sulzer Chemtech).

The temperatures in the column were measured using five Pt100
thermocouples. The reactants can be fed to the column at room
temperature or heated previously and they can be fed in two Fig. 7. Schematic diagram of reactive distillation column.
points, at the lower part of the catalyst section (L) and at the upper
part of the catalyst section (U). Distillate and bottom composi-
tions were measured by gas chromatography as it was explained 3.3.1.2. Second setup. The reactants, ethanol and acetic acid,
in the kinetic section. This column can be connected to another were fed into the column separately. Acetic acid was always
similar glass column with six glass trays. introduced in the higher section, because it is less volatile than
ethanol. The operation conditions and results of this setup are
3.3.1. Reactive distillation setups summarized in Table 6.
The operation conditions of the different runs have been
divided in two setups depending on the feed was introduced
into the column as a mixture of reactants or the reactants were Table 6
Experimental results for the first (runs 13) and second (runs 48) setup for the
fed separately (Fig. 7). reactive distillation process
First setup
3.3.1.1. First setup. The process of reactive distillation was first
analyzed with one feed, formed by ethanol and acetic acid. This 1 2 3
feed was introduced in the column in different sections (L or FHAc (mol h1 ) 3.9 3.9 3.44
U) and with different molar ratios (stechiometric ratio and with FEtOH (mol h1 ) 3 3 3.44
an acetic acid excess of 30%). The operation conditions of this Fed section L U L
setup are presented in Table 6. The value of 19 for the reflux Reflux ratio 19 19 19
xD (HAc) 0 0 0
ratio was selected to get a high hydraulic retention time.
xD (EtOH) 0.323 0.309 0.345
The molar fraction of ethyl acetate obtained is higher when xD (H2 O) 0.140 0.151 0.135
feed is introduced in the upper part of the catalyst section, since xD (EtAc) 0.535 0.540 0.520
acetic acid crosses more reaction zone (runs 1 and 2). If the Conversion % (EtOH) 54 55.3 46.7
reactants are fed in the same section (runs 1 and 3), conversion
Second setup
is higher when there is an excess of acetic acid in feed, because
the acetic acid acts as a catalyst of the reaction of esterification. 4 5 6 7 8

FHAc (mol h1 ) 3.44 6.88 8.68 8.68 8.68

Table 5 FEtOH (mol h1 ) 2.04 4.08 5.09 5.09 5.09
Azeotropic temperature and composition (molar fraction) Fed section U U U U U
System T (K) xEtAc xEtOH xH2 O Reflux ratio 19 19 19 9 4
xD (HAc) 0 0 0 0 0
Ethyl acetateethanolwater 343.25 0.587 0.159 0.254 xD (EtOH) 0.3723 0.294 0.253 0.300 0.462
Ethyl acetatewater 343.75 0.690 0.310 xD (H2 O) 0.1188 0.167 0.199 0.148 0.280
Ethyl acetateethanol 344.95 0.554 0.446 xD (EtAc) 0.5089 0.539 0.548 0.552 0.258
Ethanolwater 351.35 0.908 0.920 Conversion % (EtOH) 13.4 43.6 43.2 59.1 10
1322 N. Calvar et al. / Chemical Engineering and Processing 46 (2007) 13171323

room temperature, it could be separated by decantation. At pres-

sures below these ones, the binary azeotrope increases the molar
fraction of ethyl acetate.

4. Conclusions

The reaction kinetics of the esterification of acetic acid with

Fig. 8. Evolution of the azeotrope composition with pressure calculated with
UNIQUAC () and UNIFAC () methods.
ethanol, catalyzed both homogeneously and heterogeneously,
have been determined. Experimental data have been fitted using
the models proposed by Popken et al. [1] and the best results
have been obtained using the ASOG method to calculate the
activity coefficients.
Ethyl acetate has been obtained in a reactive distillation col-
umn and the influence of feed conditions and reflux ratio have
been investigated. The purity of ethyl acetate in distillate is
limited by the azeotrope composition. Operating at low pres-
sure, binary heterogeneous azeotrope ethyl acetatewater can
be obtained as distillate instead of ternary azeotrope.
Acknowledgment

As can be seen in Table 6, in the run 4, conversion is very The authors would like sincerely to thank to Prof. Jose
low because the feed flow is too low. Tojo Suarez, chairperson of advanced separation process group,
To study the effect of reflux ratio in the process, this was passed away recently, for his continuous dedication and valuable
changed keeping constant the rest of the variables. The reflux discussions.
ratios studied were 19, 9 and 4. With a reflux ratio higher than 9,
there is no significant change in the ethyl acetate molar fraction Appendix A. Nomenclature
obtained in the distillate composition. On the other hand, with
a reflux ratio of 4, the ethyl acetate molar fraction decreases
considerably, and the ethanol fraction in the bottom flow is zero a activity
because a so low reflux ratio takes the ethanol out of the column, EA,1 apparent activation energy (kJ mol1 )
and it cannot continue reacting. ki kinetic constant (homogeneous reaction (mol s1 ); het-
The highest molar fraction of ethyl acetate in distillate com- erogeneous reaction (mol s1 kg1 ))
position is 0.552, that is a 70% in weight fraction, similar to the ki0 preexponential factor (homogeneous reaction
result (72.2 wt.%) reported by Kloker et al. [9]. (mol s1 ); heterogeneous reaction (mol s1 kg1 ))
In the previous setups, distillation composition does not cor- m weight (g)
respond to the ternary azeotrope, so the reactive column has MRD mean relative deviation
been connected to the tray column as an additional separa- n mole number
tion unit to reach the composition of the ternary azeotrope NDAT number of data
EtAcEtOHwater. The distillated flow obtained in the packed r reaction rate (homogeneous reaction (mol s1 ); hetero-
column is fed into the tray column and the distillation compo- geneous reaction (mol s1 kg1 ))
sition obtained in this last one was xEtAc = 0.585, xEtOH = 0.160 R gas constant (J mol1 K1 )
and xwater = 0.255. SRS sum of squared residuals
To study the possibility of removing the ternary azeotrope, the T temperature (K)
evolution with pressure has been analyzed. The azeotropic com- w weight fraction
position has been predicted by UNIQUAC equation, since this is X conversion
the model that in a previous work (Calvar et al. [10]) gave better
results. This azeotrope was also studied by the UNIFAC equa- Greek letter
tion, using a simulation program. There are some differences parameter that takes into account the acid autocatalysis
in the ternary azeotrope behaviour at the different pressures, as in the homogeneous reaction
shown in Fig. 8, but the pressure where the ternary azeotrope
disappears is similar for the two methods used. The ternary Subscripts
azeotrope turns into a binary azeotrope ethyl acetatewater with calc calculated values
an approximated composition of 0.80 at 5.3 kPa for the UNI- exp experimental values
QUAC prediction and at 5 kPa for the UNIFAC prediction. The EtAc ethyl acetate
binary system ethyl acetatewater is an immiscible system in EtOH ethanol
the most composition range, so at atmospheric pressure and at HAc acetic acid
 N. Calvar et al. / Chemical Engineering and Processing 46 (2007) 13171323
H2 O water
i component i
Appendix B. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.cep.2006.10.007.
References
[1] T. Popken, L. Gotze, J. Gmehling, Reaction kinetics and chemical equilib-
rium of homogenously and heterogeneously catalyzed acetic acid esterifi-
cation with methanol and methyl acetate hydrolysis, Ind. Eng. Chem. Res.
39 (2000) 26012611.
[2] K. Kojima, K. Tochigi, Prediction of Vaporliquid Equilibria by the ASOG
Method, Elsevier, Tokyo, 1979.
[3] Aa. Fredenslund, J. Gmehling, P. Rasmussen, Vaporliquid Equilibria
Using UNIFAC. A Group Contribution Method, Elsevier, Amsterdam,
1977.
[4] H. Bock, M. Jimoh, G. Wozny, Analysis of reactive distillation using the
esterification of acetic acid as an exemple, Chem. Eng. Technol. 20 (1997)
182191.
[5] N. Vora, P. Daoutidis, Dynamics and control of an ethyl acetate reactive
distillation column, Ind. Eng. Chem. Res. 40 (2001) 833849.
[6] E.Y. Kenig, H. Bader, A. Gorak, B. Beling, T. Adrian, H. Schoenmakers,
Investigation of ethyl acetate reactive distillation process, Chem. Eng. Sci.
56 (2001) 61856193.
[7] S. Steinigeweg, J. Gmehling, N-buthyl acetate synthesis via reactive dis-
tillation: thermodynamic aspects, reaction kinetics, pilot-plant experi-
ments and simulation studies, Ind. Eng. Chem. Res. 41 (2002) 5483
5490.
1323
[8] H.T.R. Teo, B. Saha, Heterogeneous catalysed esterification of acetic acid
with isoamyl alcohol: kinetic studies, J. Catal. 228 (2004) 174182.
[9] M. Kloker, E.Y. Kenig, A. Gorak, A.P. Markusse, G. Kwant, P. Moritz,
Investigation of different column configurations for the ethyl acetate syn-
thesis via reactive distillation, Chem. Eng. Process 43 (2004) 791801.
[10] N. Calvar, A. Domnguez, J. Tojo, Vaporliquid equilibria for the qua-
ternary reactive system ethyl acetate + ethanol + water + acetic acid and
constituent binary systems ethyl acetate + ethanol, ethyl acetate + acetic
acid and water + acetic acid at 101.3 kPa, Fluid Phase Equilib. 235 (2005)
215222.
[11] S.I. Kirbaslar, Z.B. Baykal, U. Dramur, Esterification of acetic acid with
ethanol catalyzed by an acidic ion-exchange resin, Turk. J. Eng. Environ.
Sci. 25 (2001) 569577.
[12] G. Hangx, G. Kwant, H. Maessen, P. Markusse, I. Urseanu, Reac-
tion Kinetics of the Esterification of Ethanol and Acetic Acid
Towards Ethyl Acetate, Technical Report to the European Commission,
http://www.cpi.umist.ac.uk/intint/NonConf Doc.asp, 2001.
[13] M. Mazzotti, B. Neri, D. Gelosa, A. Kruglov, M. Morbidelli, Kinetics of
liquid-phase esterification catalyzed by acidic resins, Ind. Eng. Chem. Res.
36 (1997) 310.
[14] M.T. Sanz, R. Murga, S. Beltran, J.L. Cabezas, J. Coca, Autocatalyzed
and ion-exchange-resin-catalyzed esterification kinetics of lactic acid with
methanol, Ind. Eng. Chem. Res. 41 (2002) 512517.
[15] A. Chakrabarti, M.M. Sharma, Cationic ion exchange resins as catalyst,
React. Polym. 20 (1993) 145.
[16] M.J. Lee, H.T. Wu, C.H. Kang, H.M. Lin, Kinetics of catalytic esterification
of acetic acid with amyl alcohol over Amberlyst 15, Chem. Eng. Jpn. 34
(2001) 960963.
[17] W.T. Liu, C.S. Tan, Liquid-phase esterification of propionic acid with n-
butanol, Ind. Eng. Chem. Res. 40 (2001) 32813286.
[18] T.A. Peters, N.E. Benes, A. Holmen, J.T.F. Keurentjes, Comparison of
commercial solid acid catalysts for the esterification of acetic acid with
butanol, Appl. Catal. A: Gen. 297 (2006) 182188.